EP1016643B1 - Method of producing methanol - Google Patents
Method of producing methanolInfo
- Publication number
- EP1016643B1 EP1016643B1 EP98955934A EP98955934A EP1016643B1 EP 1016643 B1 EP1016643 B1 EP 1016643B1 EP 98955934 A EP98955934 A EP 98955934A EP 98955934 A EP98955934 A EP 98955934A EP 1016643 B1 EP1016643 B1 EP 1016643B1
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- European Patent Office
- Prior art keywords
- gas
- heat
- synthesis
- methanol
- feedstock
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/1516—Multisteps
- C07C29/1518—Multisteps one step being the formation of initial mixture of carbon oxides and hydrogen for synthesis
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/382—Multi-step processes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/14—Details of the flowsheet
- C01B2203/141—At least two reforming, decomposition or partial oxidation steps in parallel
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/14—Details of the flowsheet
- C01B2203/142—At least two reforming, decomposition or partial oxidation steps in series
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/14—Details of the flowsheet
- C01B2203/142—At least two reforming, decomposition or partial oxidation steps in series
- C01B2203/143—Three or more reforming, decomposition or partial oxidation steps in series
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/14—Details of the flowsheet
- C01B2203/148—Details of the flowsheet involving a recycle stream to the feed of the process for making hydrogen or synthesis gas
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/80—Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
- C01B2203/82—Several process steps of C01B2203/02 - C01B2203/08 integrated into a single apparatus
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- This invention relates to a process for producing methanol by subjecting a feedstock gas composed mainly of natural gas to primary reforming and secondary reforming to convert the feedstock gas to a synthesis gas comprising hydrogen, carbon monoxide and carbon dioxide and producing methanol from the synthesis gas.
- the Japanese Patent Laid-Open Publication No. 3614/1990 proposes to use the enthalpy of a product from the secondary reforming using oxygen, as a heat source for the primary reforming by steam.
- Plants for producing methanol from natural gas have recently been demanded to reduce costs with economical efficiency added and to further improve the energy efficiency of the whole methanol synthesis plant, in the construction of methanol plants that are significantly increasing in size due to the production of fuel methanol.
- Fig. 1 is a flowsheet of a process for producing methanol according to the present invention.
- the feedstock gas used in the present invention is a hydrocarbon gas having an atomic ratio of 3 - 4, for example, natural gas composed mainly of methane, or a hydrocarbon gas having an atomic ratio H/C of 3 - 4 obtained, as is well known, by preliminarily reforming a liquid hydrocarbon having an atomic ratio H/C of 2 - 3, such as naphtha, with steam in a prereformer at a temperature of 250 - 550°C in the presence of a catalyst composed primarily of nickel oxide by way of example.
- a hydrocarbon gas having an atomic ratio of 3 - 4 for example, natural gas composed mainly of methane, or a hydrocarbon gas having an atomic ratio H/C of 3 - 4 obtained, as is well known, by preliminarily reforming a liquid hydrocarbon having an atomic ratio H/C of 2 - 3, such as naphtha, with steam in a prereformer at a temperature of 250 - 550°C in the presence of a catalyst composed
- the primary reforming means comprises a fired-heating type steam reformer and a heat-exchange type steam reformer, and a feedstock mixed gas formed by mixing steam with the feedstock gas with sulfur removed is fed to both of the fired-heating type steam reformer and the heat-exchange type steam reformer.
- a feedstock mixed gas formed by mixing steam with the feedstock gas with sulfur removed is fed to both of the fired-heating type steam reformer and the heat-exchange type steam reformer.
- steam generated by the heat of reaction in the methanol synthesis reactor is mixed with the feedstock gas supplied to the primary reforming means.
- the amount of steam supplied from the outside can be minimized and the energy generated inside the plant can be effectively utilized.
- the heat required for the heat-exchange type steam reforming in the primary reforming is obtained by partial oxidation reaction in the secondary reforming.
- the amount of oxygen necessary to carry out the partial oxidation gives effects also on the composition of the synthesis gas having completed the secondary reforming reaction.
- the relation (R) and the load distribution between the fired-heating type steam reformer and the heat-exchange type steam reformer are so regulated that the purge gas from the methanol synthesis may substantially be balanced with the amount of fuel necessary for the fired-heating type steam reformer in the primary reforming.
- the feedstock gas with surfur removed is mixed with steam fed through a line 18.
- steam generated in a methanol synthesis reactor 29 is recovered and mixed with the feedstock gas by way of a line 41.
- the feedstock gas is supplied partially to the combustion type steam reforming furnace 22 by way of a line 17 as a desulfurized auxiliary fuel for the combustion type steam reforming furnace 22, prior to being mixed with steam.
- a feedstock mixed gas in which the feedstock gas is mixed with steam, is supplied to a heat-exchange type steam reformer 21 through a line 3 and the fired-heating type steam reformer 22 via a line 2 after being heated to about 560°C in a mixed gas heater 34.
- the proportion of the feed rate of the feedstock mixed gas sent to the heat-exchange type reformer 21 to that of the gas sent to the fired-heating type reformer 22 may be 1 to 3 - 3 to 1.
- the feedstock mixed gas in the line 3 to be sent to the heat-exchange type steam reformer 21 may first be heated in the mixed gas heater 34, if the burned gas supplied through a line 42 contains enough heat, and then be branched to the heat-exchange type steam reformer 21 from the feed line 2 to the fired-heating type steam reformer 22. Further, the feedstock mixed gas may be supplied to the heat-exchange type reformer 21 after being heated in a mixed gas heater installed separately on the line 3. Alternatively, the mixed gas may be supplied to the heat-exchange type steam reformer 21 after being heat-exchanged with a reformed gas from the same reformer 21.
- a purge gas from the methanol synthesis loop, a flash gas and auxiliary fuel are fed to the fired-heating type reformer 22 via a line 13, line 15 and line 17, respectively, and air for combustion is supplied through a line 19 so that the fuel is burned by means of low NOx burners, producing the reaction heat for the steam reforming.
- the fired-heating type steam reformer 22 is constructed by installing in parallel a plurality of reaction tubes packed with a nickel-base catalyst.
- the operating conditions at the outlet of the reaction tubes are in the range of 15 - 40 Kg/cm 2 -G in pressure and 700 - 850°C in temperature.
- An example of the conditions is such that the pressure is 19.4 Kg/cm 2 -G, the temperature is 800°C, and the residual amount of unreformed methane is 10.6 dry mol%.
- the temperature of the burned gas which has imparted the reaction heat to the tubular reactor is about 1,000°C, and the gas is sent to the mixed gas heater 34, a heat recovery unit 35 for preheating boiler water and a feedstock preheater 36 via the line 42 from the combustion type steam reforming furnace 22 to further recover the waste heat.
- the feedstock mixed gas sent to the heat-exchange type steam reformer 21 through the line 3 is given the reaction heat by exchanging heat with a synthesis gas having a temperature of 950 - 1,000°C discharged from a secondary reformer 23 to a line 7.
- the feedstock mixed gas for the heat-exchange type steam reformer 21 is passed inside the tubes where a nickel-base catalyst is packed.
- the operating conditions at the outlet of the tubes are such that the pressure is 19.4 Kg/cm 2 -G, the temperature is 820°C, and the residual amount of unreacted methane is 9.5 dry mol%, for instance.
- Synthesis gases each containing 5 - 15% of unreformed methane from the respective steam reforming reactions are sent to the secondary reformer 23 via lines 4 and 5 to reform the unreformed methane.
- Oxygen of 95 - 99% concentration is fed to the secondary reformer 23 through a line 6 by way of an air separator 33.
- the operating conditions at the outlet of the secondary reformer 23 are in the range of 15 - 40 Kg/cm 2 -G in pressure and 950 - 1,000°C in temperature, and an example of the conditions is such that the pressure is 19.0 Kg/cm 2 -G, the temperature is 950 - 1,000°C, and the residual amount of unreformed methane is 0.4 dry mol%.
- the synthesis gas is sent through a line 9 to a synthesis gas compressor 27 where it is pressurized to 40 - 100 Kg/cm 2 -G, for example, to 100 Kg/cm 2 -G.
- the pressurized synthesis gas is fed to a methanol synthesis reactor 29 by way of a line 10.
- the pressurized synthesis gas is mixed with unreacted synthesis gas discharged from a methanol separator 31 to a line 14, and is then heat-exchanged with a synthesis gas taken out from the methanol synthesis reactor 29 to a line 11, so that the mixed synthesis gas is raised in temperature to 210 - 240°C.
- the methanol synthesis reaction is carried out under the conditions of, for example, a pressure of 40 - 100 Kg/cm 2 -G and a temperature of 210 - 300°C as is well known in the art.
- boiler water is fed to the methanol synthesis reactor 29 through a line 40, and the heat of reaction is recovered as steam via a line 41.
- the steam is used as steam for steam reforming.
- An unreacted synthesis gas containing about 7% of product methanol from the methanol synthesis reactor 29 is taken out through the line 11, heat-exchanged with the synthesis gas fed to the methanol synthesis reactor 29, passed to a condenser 30 to condense the product methanol and then sent to a methanol separator 31 to separate the condensed crude methanol from the unreacted synthesis gas.
- the most part of the unreacted synthesis gas is circulated to the methanol synthesis reactor 29 by means of a circulating compressor 28, while the rest is sent to the combustion type steam reforming furnace 22 via a line 13 as a purge gas to remove accumulated inert components so that it is effectively utilized in the furnace 22 as fuel.
- the crude methanol of a line 12 separated in the methanol separator 31 contains gaseous components dissolved under high pressure, it is flashed by reducing pressure in a let-down drum 32 to discharge the dissolved gaseous components to a line 15, the flash gas being also used as a fuel for the combustion type reforming furnace 22.
- the crude methanol with the dissolved gas removed is sent to a methanol refining unit through a line 16.
- the present invention is illustrated in detail by referring to the following Examples and Comparative Examples in each of which a methanol plant of 10,000 tons per day production is designed.
- Natural gas of the following composition is used as a feedstock.
- a combustion type steam reforming furnace and a heat-exchange type steam reformer are used as primary reforming units.
- Oxygen from an air separator is employed in secondary reforming.
- Process design parameters are regulated so that the relation (R) among the mol percentages of CO 2, CO and H 2 in the synthesis gas may become 2.5, and production of the synthesis gas and synthesis of methanol are carried out under the conditions described below.
- Table 1 The material balance is shown in Table 1.
- the vertical column represents the number of each line given in Fig. 1, while the horizontal column shows the pressure, temperature, flow rate, and composition of substances flowing through each line.
- Table 1 Line number Pressure Kg/cm 2 -G Temp. °C Composition (mol %) Flow rate kmol/hr CH 4 H 2 CO CO 2 O 2 N 2 H 2 O CH 3 OH C 2 H 6 C 3 H 8
- Others 1 27.0 40 98.50 1.00 0.50 13,492.5 2 25.0 560 27.75 71.83 0.28 0.14 26,045.9 3 25.0 340 27.75 71.83 0.28 0.14 21,852.5 4 19.4 800 7.15 46.49 7.93 5.77 32.66 35,883.5 5 19.4 819 6.49 47.42 8.67 5.45 31.96 30,455.8 6 20.0 150 99.00 1.00 3,265.2 7 19.0 975 0.39 49.90 13.06 4.93 0.04 31.67 74,869.2 9 17.0 40 0.57 72
- the energy efficiency of the whole plant was as shown in Table 6, and the overall unit energy consumption [G(giga)cal/ton-methanol] was 6.692. CH 4 98.50 mol% C 2 H 6 1.00 mol% C 3 H 8 0.50 mol% Distribution rate to primary reforming Combustion type steam reforming furnace 54.4% Heat-exchange type steam reformer 45.6% Catalyst composition in combustion type steam reforming furnace Ni 20 ⁇ 2 wt% Al 2 O 3 72 to 75 wt% CaO ⁇ 0.10 wt% TiO 2 ⁇ 0.05 wt% SiO 2 ⁇ 0.01 wt% Oxygen supply to secondary reformer Flow rate 73,186 Nm 3 /hour Purity 99.0 %
- the energy efficiency of the whole plant was as shown in Table 6, and the overall unit energy consumption (Gcal/ton-methanol) was 6.714.
- the unit energy consumption was improved by 1.40% as compared with Comparative Example 2 of a conventional process. Further, the amount of fuel required for the fired-hearting type reformer and the net consumption of fuel natural gas were reduced in comparison with Comparative Example 2.
- Example 3 Operation was carried out under the same conditions as in Example 1 except that natural gas of the same composition as used in Example 2 was employed as a feedstock and process design parameters were so regulated that the relation (R) among the mol percentages of CO 2 , CO and H 2 in the synthesis gas may become 2.25.
- the material balance is shown in Table 3. Distribution rate to primary reforming means Fired-heating type steam reformer 30.6% Heat-exchange type steam reformer 69.4%
- the energy efficiency of the whole plant was as shown in Table 6, and the overall unit energy consumption (Gcal/ton-methanol) was 6.711.
- the unit energy consumption was improved by 1.45% as compared with Comparative Example 2 of a conventional process. Further, the amount of fuel required for the fired-heating type reformer and the net consumption of fuel natural gas were reduced in comparison with Comparative Example 2.
- Table 3 Line number Pressure Kg/cm 2 -G Temp.
- Example 4 Operation was carried out under the same conditions as in Example 1, except that natural gas of the same composition as used in Example 2 was employed as a feedstock and process design parameters were so regulated that the relation (R) among the mol percentages of CO 2 , CO and H 2 in the synthesis gas may become 2.0.
- the material balance is shown in Table 4. Distribution rate to primary reforming means Fired-heating type steam reformer 4.1% Heat-exchange type steam reformer 95.9% Table 4 Line number Pressure Kg/cm 2 -G Temp.
- the energy efficiency of the whole plant was as shwon in Table 6, and the overall unit energy consumption (Gcal/ton-methanol) was 6.848.
- the unit energy consumption was degraded by 0.57% as compared with Comparative Example 2 of a conventional process.
- the amount of oxygen required and the total power requirements were increased in comparison with Example 1, Example 2 and Comparative Example 2.
- Example 5 Operation was carried out under the same conditions as in Example 1 except that the primary reforming means was carried out in the conventional manner using only a fired-heating type steam reformer, natural gas of the same composition as used in Example 2 being employed as a feedstock, and process design parameters were so regulated that the relation (R) among the mol percentages of CO 2 , CO and H 2 in the synthesis gas may become 2.5.
- the material balance is shown in Table 5.
- Table 5 Line number Pressure Kg/cm 2 -G Temp.
- the energy efficiency of the whole plant was as shown in Table 6, and the overall unit energy consumption (Gcal/ton-methanol) was 6.809. In this case, however, the amount of heat recovered from the process exceeds significantly the total power requirements of rotary machines, so that if the excess energy is not sold to the outside, it cannot contribute to the accomplishment of the unit energy consumption described above.
- Example 1 Example 2 Example 3 Camp.Ex.1 Comp.Ex.2 Relation (R) among mol% of H 2 , CO and CO 2 in synthesis gas 2.5 2.5 2.25 2.0 2.5 Consumtion of feedstock natural gas (Gcal/t-methanol) 1 6.306 6.255 6.132 6.132 6.255 Fuel requirements of fired-heating type reformer (Gcal/hr) 321.04 653.64 334.01 43.92 1,223.21 Amount of purge gas for fuel (Gcal/hr) -517.53 -520.44 -275.26 -47.99 -520.44 Net consumption of fuel natural gas (Gcal/hr) 106.30 133.20 58.75 -4.07 702.77 Net consumption of fuel natural gas (Gcal/t-methanol) 2 0.227 0.320 0.141 -0.010 1.687 Oxygen requirements (Nm 3 /hr) 73,186 66,222 102,716 138.806 66,222 Amount of synthesis make-up gas (Nm 3
- the energy efficiency of a whole process for the production of methanol including the production of synthesis gas is improved in comparison with the conventional processes and the construction cost of the process plant is also reduced.
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Description
- This invention relates to a process for producing methanol by subjecting a feedstock gas composed mainly of natural gas to primary reforming and secondary reforming to convert the feedstock gas to a synthesis gas comprising hydrogen, carbon monoxide and carbon dioxide and producing methanol from the synthesis gas.
- Processes for producing methanol from hydrogen and carbon oxides are based on the following two reactions:
CO + 2H2 = CH3OH
CO2 + 3H2 = CH3OH + H2O
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- Consequently, it is common to think that a synthesis gas, which has a composition very close or equivalent to the aforesaid stoichiometric composition demanded for methanol synthesis, namely, a composition that makes R = 2.0, should be produced.
- As a conventional process, Japanese Patent Publication No. 46961/1980 discloses a process which comprises dividing a feedstock gas into two streams, subjecting one of the streams to conventional steam reforming to form an effluent gas, combining the effluent gas with the other stream, and subjecting the combined stream to secondary reforming using oxygen, thereby producing a synthesis gas having the stoichiometric composition (R = 2.0) suitable for methanol synthesis. Further, the Japanese Patent Laid-Open Publication No. 3614/1990 proposes to use the enthalpy of a product from the secondary reforming using oxygen, as a heat source for the primary reforming by steam.
- However, when R is made 2.0 as in the above prior art processes, loss of energy is increased due to increase in the consumption of oxygen, though the energy for compressing the synthesis gas is reduced.
- Further, as a process to solve the problems of the above prior art processes, Japanese Patent Laid-Open Publication No. 4140/1985 teaches a process for producing a methanol synthesis gas from natural gas as a feedstock through primary steam reforming and secondary oxygen combustion reforming, wherein the primary reforming conditions, secondary reforming conditions and amount of oxygen supply are so created that the synthesis gas may have a composition of R = 2.2 - 2.5 and in consequence the energy efficiency of the whole plant including oxygen production, synthesis gas production and methanol synthesis becomes higher than that of the case of R = 2.0.
- However, this process involves a problem of limits in fabricating the combustion-type steam reforming furnace used in the primary steam reforming and a problem of reliability for the uniform distribution of the feedstock into a large number, such as more than a thousand, of reaction tubes.
- Further, the aforesaid process of Japanese Patent Laid-Open Publication No. 3614/1990 has no combustion system for effectively burning purge gas from the synthesis loop as a fuel within the process system. Therefore, it needs new installation of a gas turbine and requires large plant investments to maintain the efficiency of the system. In addition, the process cannot maintain its efficiency unless it sells excess heat to the outside by way of means such as exportation of power as occasion demands.
- Plants for producing methanol from natural gas have recently been demanded to reduce costs with economical efficiency added and to further improve the energy efficiency of the whole methanol synthesis plant, in the construction of methanol plants that are significantly increasing in size due to the production of fuel methanol.
- It is an object of the present invention to provide a process for producing methanol which improves the energy efficiency of a whole plant for the synthesis of methanol including the production of methanol synthesis gas.
- As a result of intensive investigation to solve the aforesaid problems of the prior art, the inventors have found that the energy efficiency of the whole plant is significantly improved by the process described below.
- The process for producing methanol according to the present invention is a process which comprises subjecting a feedstock gas comprising hydrocarbons having atomic ratios H/C of hydrogen (H) to carbon (C) of 3 - 4 or a feedstock gas formed by treating hydrocarbons having atomic ratios H/C of 2 - 3 in a prereformer to primary reforming under the conditions of a pressure of 15 - 40 Kg/cm2-G, a catalyst a outlet temperature of 700 - 850°C and a molar ratio S/C of steam (S) to carbon in the feedstock gas of 2.5 - 4.0 and then to secondary reforming using oxygen having a purity of 95% or more under the conditions of a pressure of 15 - 40 Kg/cm2-G and a catalyst outlet temperature of 950 - 1,000°C to obtain a synthesis gas in which the relation (R) among the mol percentages of hydrogen, carbon monoxide and carbon dioxide is 2.2 - 2.5 as calculated according to the following equation
- Fig. 1 is a flowsheet of a process for producing methanol according to the present invention.
- The feedstock gas used in the present invention is a hydrocarbon gas having an atomic ratio of 3 - 4, for example, natural gas composed mainly of methane, or a hydrocarbon gas having an atomic ratio H/C of 3 - 4 obtained, as is well known, by preliminarily reforming a liquid hydrocarbon having an atomic ratio H/C of 2 - 3, such as naphtha, with steam in a prereformer at a temperature of 250 - 550°C in the presence of a catalyst composed primarily of nickel oxide by way of example.
- In the present invention, the primary reforming means comprises a fired-heating type steam reformer and a heat-exchange type steam reformer, and a feedstock mixed gas formed by mixing steam with the feedstock gas with sulfur removed is fed to both of the fired-heating type steam reformer and the heat-exchange type steam reformer. By controlling the rates of feed in a proportion of 1 to 3 - 3 to 1, it becomes possible for the fired-heating type steam reformer to use a part of unreacted synthesis gas generated in the methanol synthesis loop and a flash gas as the greater part of the fuel. Separately, in the heat-exchange type steam reformer, it has become possible to utilize a synthesis gas having completed the secondary reforming reaction to exchange heat with the feedstock mixed gas.
- In the present invention, steam generated by the heat of reaction in the methanol synthesis reactor is mixed with the feedstock gas supplied to the primary reforming means. As a result, the amount of steam supplied from the outside can be minimized and the energy generated inside the plant can be effectively utilized.
- Further, the enthalpy of the product from the secondary reforming is used as a heat source to furnish 1/4 - 3/4 of the heat quantity required for the primary steam reforming, and the amount of oxygen supply is so set that the synthesis gas may have a composition of R = 2.2 - 2.5 to regulate the purge gas from the synthesis to be substantially balanced with the amount of fuel necessary for the combustion type steam reforming furnace of the primary reforming. Consequently, the fuel required for the primary reforming is saved and the compression power for oxygen can be reduced, improving the energy efficiency of the whole plant by 1 - 2%.
- Where the enthalpy of the product from the secondary reforming is used as a heat source to furnish 1/4 or less of the heat quantity required for the primary reforming, it cannot be expected to save 10% or more of the fuel required for the primary reforming, while on the ontrary where 3/4 or more of the heat quantity is furnished by the enthalpy, it becomes impossible to produce a synthesis gas of R = 2.2 - 2.5.
- The heat required for the heat-exchange type steam reforming in the primary reforming is obtained by partial oxidation reaction in the secondary reforming. The amount of oxygen necessary to carry out the partial oxidation gives effects also on the composition of the synthesis gas having completed the secondary reforming reaction.
- Therefore, where the amount of oxygen supply is so set that the synthesis gas may have a composition of R = 2.2 - 2.5, the load of the heat-exchange type steam reformer being determined, and the distribution of the feedstock mixed gas is determined, the relation (R) and the load distribution between the fired-heating type steam reformer and the heat-exchange type steam reformer are so regulated that the purge gas from the methanol synthesis may substantially be balanced with the amount of fuel necessary for the fired-heating type steam reformer in the primary reforming.
- Then, the present invention is illustrated in detail with reference to Fig. 1. A feedstock gas composed primarily of methane, such as natural gas, is supplied through a line 1, raised in temperature to a desulfurization temperature of about 400°C by a feedstock preheater 36, in which the waste heat of a combustion gas from a combustion type steam reforming furnace 22 is utilized, and fed to a desulfurizer 20 to remove completely sulfur, that is a catalyst poison of steam reforming catalysts. The feedstock gas with surfur removed is mixed with steam fed through a line 18. At the same time, steam generated in a methanol synthesis reactor 29 is recovered and mixed with the feedstock gas by way of a line 41. In consequence, it is sufficient if the steam fed through the line 18 from the outside makes up only the deficit between the amount of steam necessary in the primary reforming means and that of the steam through the line 41. This may save about 70% of the amount of steam required in the prior art processes.
- The feedstock gas is supplied partially to the combustion type steam reforming furnace 22 by way of a line 17 as a desulfurized auxiliary fuel for the combustion type steam reforming furnace 22, prior to being mixed with steam.
- A feedstock mixed gas, in which the feedstock gas is mixed with steam, is supplied to a heat-exchange type steam reformer 21 through a line 3 and the fired-heating type steam reformer 22 via a line 2 after being heated to about 560°C in a mixed gas heater 34. The proportion of the feed rate of the feedstock mixed gas sent to the heat-exchange type reformer 21 to that of the gas sent to the fired-heating type reformer 22 may be 1 to 3 - 3 to 1.
- Although not shown in the drawing, the feedstock mixed gas in the line 3 to be sent to the heat-exchange type steam reformer 21 may first be heated in the mixed gas heater 34, if the burned gas supplied through a line 42 contains enough heat, and then be branched to the heat-exchange type steam reformer 21 from the feed line 2 to the fired-heating type steam reformer 22. Further, the feedstock mixed gas may be supplied to the heat-exchange type reformer 21 after being heated in a mixed gas heater installed separately on the line 3. Alternatively, the mixed gas may be supplied to the heat-exchange type steam reformer 21 after being heat-exchanged with a reformed gas from the same reformer 21.
- As the fuel for the fired-heating type steam reformer 22, a purge gas from the methanol synthesis loop, a flash gas and auxiliary fuel are fed to the fired-heating type reformer 22 via a line 13, line 15 and line 17, respectively, and air for combustion is supplied through a line 19 so that the fuel is burned by means of low NOx burners, producing the reaction heat for the steam reforming. The fired-heating type steam reformer 22 is constructed by installing in parallel a plurality of reaction tubes packed with a nickel-base catalyst. The operating conditions at the outlet of the reaction tubes are in the range of 15 - 40 Kg/cm2-G in pressure and 700 - 850°C in temperature. An example of the conditions is such that the pressure is 19.4 Kg/cm2-G, the temperature is 800°C, and the residual amount of unreformed methane is 10.6 dry mol%.
- The temperature of the burned gas which has imparted the reaction heat to the tubular reactor is about 1,000°C, and the gas is sent to the mixed gas heater 34, a heat recovery unit 35 for preheating boiler water and a feedstock preheater 36 via the line 42 from the combustion type steam reforming furnace 22 to further recover the waste heat.
- Separately, the feedstock mixed gas sent to the heat-exchange type steam reformer 21 through the line 3 is given the reaction heat by exchanging heat with a synthesis gas having a temperature of 950 - 1,000°C discharged from a secondary reformer 23 to a line 7. The feedstock mixed gas for the heat-exchange type steam reformer 21 is passed inside the tubes where a nickel-base catalyst is packed. The operating conditions at the outlet of the tubes are such that the pressure is 19.4 Kg/cm2-G, the temperature is 820°C, and the residual amount of unreacted methane is 9.5 dry mol%, for instance.
- Synthesis gases each containing 5 - 15% of unreformed methane from the respective steam reforming reactions are sent to the secondary reformer 23 via lines 4 and 5 to reform the unreformed methane. Oxygen of 95 - 99% concentration is fed to the secondary reformer 23 through a line 6 by way of an air separator 33. The amount of oxygen supply is so regulated that the relation (R) among the mol percentages of hydrogen, carbon monoxide and carbon dioxide, that are a composition of the synthesis gas at the outlet of the secondary reformer, may become 2.2 - 2.5 as calculated according to the following equation:
- The operating conditions at the outlet of the secondary reformer 23 are in the range of 15 - 40 Kg/cm2-G in pressure and 950 - 1,000°C in temperature, and an example of the conditions is such that the pressure is 19.0 Kg/cm2-G, the temperature is 950 - 1,000°C, and the residual amount of unreformed methane is 0.4 dry mol%. The synthesis gas, passed through the shell-side of the heat-exchange type reformer 21 via the line 7 to furnish the reaction heat of the steam reforming, is sent through a line 8 to a heat recovery unit 24 for preheating boiler water, to a cooler 25 to condense water, and then to a condensed water separator 26 to separate the condensed water.
- The synthesis gas is sent through a line 9 to a synthesis gas compressor 27 where it is pressurized to 40 - 100 Kg/cm2-G, for example, to 100 Kg/cm2-G. The pressurized synthesis gas is fed to a methanol synthesis reactor 29 by way of a line 10. However, before being fed to the methanol synthesis reactor 29, the pressurized synthesis gas is mixed with unreacted synthesis gas discharged from a methanol separator 31 to a line 14, and is then heat-exchanged with a synthesis gas taken out from the methanol synthesis reactor 29 to a line 11, so that the mixed synthesis gas is raised in temperature to 210 - 240°C.
- The methanol synthesis reaction is carried out under the conditions of, for example, a pressure of 40 - 100 Kg/cm2-G and a temperature of 210 - 300°C as is well known in the art. Here, boiler water is fed to the methanol synthesis reactor 29 through a line 40, and the heat of reaction is recovered as steam via a line 41. The steam is used as steam for steam reforming.
- An unreacted synthesis gas containing about 7% of product methanol from the methanol synthesis reactor 29 is taken out through the line 11, heat-exchanged with the synthesis gas fed to the methanol synthesis reactor 29, passed to a condenser 30 to condense the product methanol and then sent to a methanol separator 31 to separate the condensed crude methanol from the unreacted synthesis gas. The most part of the unreacted synthesis gas is circulated to the methanol synthesis reactor 29 by means of a circulating compressor 28, while the rest is sent to the combustion type steam reforming furnace 22 via a line 13 as a purge gas to remove accumulated inert components so that it is effectively utilized in the furnace 22 as fuel. If inert methane and nitrogen are accumulated in large amounts within the synthesis loop, the partial pressures of hydrogen, carbon monoxide and carbon dioxide in the methanol synthesis reactor 29 are reduced so that adequate amounts of the inert components have to be purged from the circulation loop to prevent the efficiency of the methanol synthesis from degrading.
- Since the crude methanol of a line 12 separated in the methanol separator 31 contains gaseous components dissolved under high pressure, it is flashed by reducing pressure in a let-down drum 32 to discharge the dissolved gaseous components to a line 15, the flash gas being also used as a fuel for the combustion type reforming furnace 22.
- Separately, the crude methanol with the dissolved gas removed is sent to a methanol refining unit through a line 16.
- The present invention is illustrated in detail by referring to the following Examples and Comparative Examples in each of which a methanol plant of 10,000 tons per day production is designed.
- Natural gas of the following composition is used as a feedstock. A combustion type steam reforming furnace and a heat-exchange type steam reformer are used as primary reforming units. Oxygen from an air separator is employed in secondary reforming. Process design parameters are regulated so that the relation (R) among the mol percentages of CO2, CO and H2 in the synthesis gas may become 2.5, and production of the synthesis gas and synthesis of methanol are carried out under the conditions described below.
- The material balance is shown in Table 1. The vertical column represents the number of each line given in Fig. 1, while the horizontal column shows the pressure, temperature, flow rate, and composition of substances flowing through each line.
Table 1 Line number Pressure Kg/cm2-G Temp. °C Composition (mol %) Flow rate kmol/hr CH4 H2 CO CO2 O2 N2 H2O CH3OH C2H6 C3H8 Others 1 27.0 40 98.50 1.00 0.50 13,492.5 2 25.0 560 27.75 71.83 0.28 0.14 26,045.9 3 25.0 340 27.75 71.83 0.28 0.14 21,852.5 4 19.4 800 7.15 46.49 7.93 5.77 32.66 35,883.5 5 19.4 819 6.49 47.42 8.67 5.45 31.96 30,455.8 6 20.0 150 99.00 1.00 3,265.2 7 19.0 975 0.39 49.90 13.06 4.93 0.04 31.67 74,869.2 9 17.0 40 0.57 72.73 19.04 7.18 0.06 0.42 51,369.5 10 100.0 240 2.59 88.31 5.40 3.00 0.31 0.07 0.30 0.02 228,299.1 11 98.0 260 2.93 85.01 1.32 1.69 0.35 1.79 6.80 0.02 202,112.1 12 96.0 40 0.18 0.41 0.04 0.61 0.01 21.19 77.47 0.10 16,797.2 13 96.0 40 3.18 92.77 1.44 1.79 0.38 0.04 0.39 0.02 8,265.0 14 96.0 40 3.18 92.77 1.44 1.79 0.38 0.04 0.39 0.02 177,049.9 15 3.5 40 15.73 46.84 3.76 22.28 0.74 0.57 6.36 3.71 143.1 16 3.5 40 0.05 0.01 0.01 0.42 0.00 21.36 78.08 0.07 16,654.1 17 3.5 400 98.50 1.00 0.50 479.5 41 29.0 233 100.00 25,452.2 - The energy efficiency of the whole plant was as shown in Table 6, and the overall unit energy consumption [G(giga)cal/ton-methanol] was 6.692.
CH4 98.50 mol% C2H6 1.00 mol% C3H8 0.50 mol% Distribution rate to primary reforming Combustion type steam reforming furnace 54.4% Heat-exchange type steam reformer 45.6% Catalyst composition in combustion type steam reforming furnace Ni 20 ± 2 wt% Al2O3 72 to 75 wt% CaO < 0.10 wt% TiO2 < 0.05 wt% SiO2 < 0.01 wt% Oxygen supply to secondary reformer Flow rate 73,186 Nm3/hour Purity 99.0 % -
R = (H2 - CO2)/(CO + CO2) = 2.50
-
Upper heat-resistant catalyst Cr2O3 6 ± 2 wt% Al2O3 95 to 97 wt% CaO < 0.10 wt% TiO2 < 0.05 wt% SiO2 < 0.10 wt% Lower reforming catalyst Ni 16 ± 1 wt% Al2O3 95 to 97 wt% CaO 0.10 wt% Ti 3.00 wt% SiO2 0.20 wt% -
Composition of catalyst used CuO 20 to 50 wt% ZnO 15 to 60 wt% Al2O3 5 to 30 wt% MgO 0.2 to 7 wt% Temperature of catalyst bed 240 to 260°C - Operation was carried out in the same manner as in Example 1, except that natural gas of the following composition was used as a feedstock. The material balance is shown in Table 2.
- The energy efficiency of the whole plant was as shown in Table 6, and the overall unit energy consumption (Gcal/ton-methanol) was 6.714. The unit energy consumption was improved by 1.40% as compared with Comparative Example 2 of a conventional process. Further, the amount of fuel required for the fired-hearting type reformer and the net consumption of fuel natural gas were reduced in comparison with Comparative Example 2.
Natural gas composition CH4 95.60 mol% C2H6 3.39 mol% C3H8 0.09 mol% C4H10 0.03 mol% C5H12 0.01 mol% C6H14 0.14 mol% N2 0.26 mol% CO2 0.47 mol% H2O 0.01 mol% Distribution rate to primary reforming means Fired-heating type steam reformer 58.7% Heat-exchange type steam reformer 41.3% Table 2 Line number Pressure Kg/cm2-G Temp. °C Composition (mol %) Flow rate kmol/hr CH4 H2 CO CO2 O2 N2 H2O CH3OH C2H6 C3H8 Others 1 27.0 40 95.60 0.47 0.26 0.01 3.39 0.09 0.18 13,236.3 2 25.0 560 26.62 0.13 0.07 72.16 0.94 0.03 0.05 27,904.2 3 25.0 360 26.62 0.13 0.07 72.16 0.94 0.03 0.05 19,632.8 4 19.4 800 7.17 46.04 8.09 5.76 0.05 32.89 38,494.7 5 19.4 846 4.95 49.73 5.19 4.95 0.05 30.02 28,178.4 6 20.0 150 99.00 1.00 2,984.4 7 19.0 975 0.41 50.18 13.23 4.89 0.09 31.32 74,399.3 9 17.0 40 0.59 72.64 19.15 7.08 0.13 0.41 51,389.8 10 100.0 240 2.67 87.87 5.41 3.00 0.60 0.12 0.30 0.02 229,493.1 11 98.0 260 3.02 84.65 1.33 1.81 0.68 1.81 6.76 0.02 203,305.1 12 96.0 40 0.19 0.40 0.04 0.62 0.06 21.45 77.18 0.10 16,859.9 13 96.0 40 3.27 92.26 1.45 1.83 0.39 0.74 0.39 0.02 8,342.0 14 96.0 40 3.27 92.26 1.45 1.83 0.39 0.74 0.39 0.02 168,859.9 15 3.5 40 23.26 45.68 3.72 22.63 1.42 0.83 6.34 3.66 145.7 16 3.5 40 0.05 0.01 0.00 0.43 0.00 21.64 77.80 0.07 16,714.2 17 3.5 400 95.60 0.47 0.26 0.01 3.39 0.09 0.18 684.0 41 29.0 233 100.00 25,081.8 - Operation was carried out under the same conditions as in Example 1 except that natural gas of the same composition as used in Example 2 was employed as a feedstock and process design parameters were so regulated that the relation (R) among the mol percentages of CO2, CO and H2 in the synthesis gas may become 2.25. The material balance is shown in Table 3.
Distribution rate to primary reforming means Fired-heating type steam reformer 30.6% Heat-exchange type steam reformer 69.4% - The energy efficiency of the whole plant was as shown in Table 6, and the overall unit energy consumption (Gcal/ton-methanol) was 6.711. The unit energy consumption was improved by 1.45% as compared with Comparative Example 2 of a conventional process. Further, the amount of fuel required for the fired-heating type reformer and the net consumption of fuel natural gas were reduced in comparison with Comparative Example 2.
Table 3 Line number Pressure Kg/cm2-G Temp. °C Composition (mol %) Flow rate kmol/hr CH4 H2 CO CO2 O2 N2 H2O CH3OH C2H6 C3H8 Others 1 27.0 40 95.60 0.47 0.26 0.01 3.39 0.09 0.18 12,975.1 2 25.0 560 26.62 0.13 0.07 72.16 0.94 0.03 0.05 14,259.2 3 25.0 360 26.62 0.13 0.07 72.16 0.94 0.03 0.05 32,339.4 4 19.4 800 7.17 46.04 8.09 5.76 0.05 32.89 19,671.0 5 19.4 726 12.45 36.41 4.25 6.26 0.06 40.57 40,840.5 6 20.0 150 99.00 1.00 4,629.1 7 19.0 975 0.28 46.54 12.59 5.60 0.11 34.87 73,137.9 9 17.0 40 0.43 71.17 19.26 8.57 0.17 0.41 47,827.5 10 100.0 240 3.24 87.20 4.68 3.00 0.31 0.11 0.31 0.02 254,243.3 11 98.0 260 3.61 84.01 1.21 1.62 1.61 1.21 6.06 0.02 228,095.6 12 96.0 40 0.21 0.37 0.03 0.57 0.03 23.85 74.84 0.09 17,388.1 13 96.0 40 3.89 90.91 1.31 1.71 1.74 1.31 0.39 0.02 4,291.7 14 96.0 40 3.89 90.91 1.31 1.71 1.74 1.31 0.39 0.02 206,415.8 15 3.5 40 18.60 43.34 3.30 21.14 0.63 3.30 6.18 3.53 146.8 16 3.5 40 0.05 0.01 0.00 0.39 0.00 24.05 75.43 0.06 17,241.3 17 3.5 400 95.60 0.47 0.26 0.01 3.39 0.09 0.18 301.7 41 29.0 233 100.00 24,082.4 - Operation was carried out under the same conditions as in Example 1, except that natural gas of the same composition as used in Example 2 was employed as a feedstock and process design parameters were so regulated that the relation (R) among the mol percentages of CO2, CO and H2 in the synthesis gas may become 2.0. The material balance is shown in Table 4.
Distribution rate to primary reforming means Fired-heating type steam reformer 4.1% Heat-exchange type steam reformer 95.9% Table 4 Line number Pressure Kg/cm2-G Temp. °C Composition (mol %) Flow rate kmol/hr CH4 H2 CO CO2 O2 N2 H2O CH3OH C2H6 C3H8 Others 1 27.0 40 95.60 0.47 0.26 0.21 3.39 0.09 0.18 12,795.2 2 25.0 560 26.26 0.13 0.07 72.16 0.94 0.03 0.05 1,874.9 3 25.0 368 26.26 0.13 0.07 72.16 0.94 0.03 0.05 44,077.6 4 19.4 800 7.17 46.04 8.09 5.76 0.05 32.89 2,586.4 5 19.4 660 16.59 28.11 1.98 5.92 47.34 522,201.6 6 20.0 150 99.00 1.00 6,255.4 7 19.0 975 0.19 42.86 11.89 6.36 0.13 38.53 72,273.9 9 17.0 40 0.30 69.49 19.28 10.31 0.21 0.41 44,575.9 10 100.0 240 8.21 72.69 3.79 3.00 11.34 0.10 0.38 0.02 340,623.2 11 98.0 260 9.43 69.00 1.35 1.85 12.28 1.54 4.55 0.02 324,496.9 12 96.0 40 0.50 0.29 0.03 0.59 0.22 26.02 72.25 0.09 18,018.4 13 96.0 40 9.97 73.18 1.43 1.90 13.01 0.05 0.44 0.02 431.3 14 96.0 40 9.97 73.18 1.43 1.90 13.01 0.05 0.44 0.02 296,047.3 15 3.5 40 31.88 21.78 2.33 19.16 15.72 0.70 6.15 2.29 236.7 16 3.5 40 0.09 0.00 0.00 0.34 0.01 26.45 73.39 0.06 17,719.7 17 41 29.0 233 100.00 22,108.5 - The energy efficiency of the whole plant was as shwon in Table 6, and the overall unit energy consumption (Gcal/ton-methanol) was 6.848. The unit energy consumption was degraded by 0.57% as compared with Comparative Example 2 of a conventional process. The amount of oxygen required and the total power requirements were increased in comparison with Example 1, Example 2 and Comparative Example 2.
- Operation was carried out under the same conditions as in Example 1 except that the primary reforming means was carried out in the conventional manner using only a fired-heating type steam reformer, natural gas of the same composition as used in Example 2 being employed as a feedstock, and process design parameters were so regulated that the relation (R) among the mol percentages of CO2, CO and H2 in the synthesis gas may become 2.5. The material balance is shown in Table 5.
Table 5 Line number Pressure Kg/cm2-G Temp. °C Composition (mol %) Flow rate kmol/hr CH4 H2 CO CO2 O2 N2 H2O CH3OH C2H6 C3H8 Others 1 27.0 40 95.60 0.47 0.26 0.01 3.39 0.09 0.18 13,236.3 2 25.0 560 26.62 0.13 0.07 72.16 0.94 0.03 0.05 47,537.0 3 4 19.4 777 6.23 47.60 8.93 5.52 0.05 31.68 66,673.1 5 6 20.0 150 99.00 1.00 2,984.4 7 19.0 975 0.41 50.18 13.23 4.89 0.09 31.32 74,399.3 9 17.0 40 0.59 72.64 19.15 7.08 0.13 0.41 51,389.8 10 100.0 240 2.67 87.87 5.41 3.00 0.60 0.12 0.30 0.02 229,493.1 11 98.0 260 3.02 84.65 1.33 1.81 0.68 1.81 6.76 0.02 203,305.1 12 96.0 40 0.19 0.40 0.04 0.62 0.06 21.45 77.18 0.10 16,859.9 13 96.0 40 3.27 92.26 1.45 1.83 0.39 0.74 0.39 0.02 8,342.0 14 96.0 40 3.27 92.26 1.45 1.83 0.39 0.74 0.39 0.02 168,859.9 15 3.5 40 23.26 45.68 3.72 22.63 1.42 0.83 6.34 3.66 145.7 16 3.5 40 0.05 0.01 0.00 0.43 0.00 21.64 77.80 0.07 16,714.2 17 3.5 400 95.60 0.47 0.26 0.01 3.39 0.09 0.18 3,608.9 41 29.0 233 100.00 25,081.8 - The energy efficiency of the whole plant was as shown in Table 6, and the overall unit energy consumption (Gcal/ton-methanol) was 6.809. In this case, however, the amount of heat recovered from the process exceeds significantly the total power requirements of rotary machines, so that if the excess energy is not sold to the outside, it cannot contribute to the accomplishment of the unit energy consumption described above.
Table 6 Example 1 Example 2 Example 3 Camp.Ex.1 Comp.Ex.2 Relation (R) among mol% of H2, CO and CO2 in synthesis gas 2.5 2.5 2.25 2.0 2.5 Consumtion of feedstock natural gas (Gcal/t-methanol) ① 6.306 6.255 6.132 6.132 6.255 Fuel requirements of fired-heating type reformer (Gcal/hr) 321.04 653.64 334.01 43.92 1,223.21 Amount of purge gas for fuel (Gcal/hr) -517.53 -520.44 -275.26 -47.99 -520.44 Net consumption of fuel natural gas (Gcal/hr) 106.30 133.20 58.75 -4.07 702.77 Net consumption of fuel natural gas (Gcal/t-methanol) ② 0.227 0.320 0.141 -0.010 1.687 Oxygen requirements (Nm3/hr) 73,186 66,222 102,716 138.806 66,222 Amount of synthesis make-up gas (Nm3/hr) 1,151,396 1,151,851 1,072,005 999,125 1,151,851 Power requirements of air compresson (kW) A 18,500 16,740 25,965 35,087 16,740 Power requirements of oxygen compressor (kW) B 10,355 9,370 14,533 19,639 9,370 Power requirements of synthesis gas/circulating gas compressor (kW) C 53,599 53,639 50,674 49,146 53,639 Total power requirements (kW) A + B + C 82,454 79,749 91,171 103,873 79,749 Energy consumption corresponding to power requirements (Gcal/t-methanol) ③ 0.567 0.549 0.627 0.715 0.549 Process heat recovery (Gcal/t-methanol) ④ -0.408 -0.410 -0.189 0.011 -1.682 Overall unit energy consumption (Gcal/t-methanol) ①+②+③+④ 6.692 6.714 6.711 6.848 6.809 - As illustrated in Table 6, it has become clear that it does not necessarily optimize the overall energy efficiency of the methanol plant to produce a synthesis gas having a molar relation among CO2, CO and H2 called the stoichiometric ratio (R = 2) in the methanol synthesis. Namely, as the relation (R) becomes smaller, the amount of oxygen required is increased and the power requirements of the air compressor to supply air to the air separation unit and the power requirements of the oxygen compressor are also increased correspondingly.
- In other words, as the relation (R) is closer to the stoichiometric ratio, power requirements of the compressor for the synthesis make-up gas is reduced. However, the total power consumption, together with the power requirements of the air compressor and the oxygen compressor, is increased offsetting the above-mentioned power reduction.
- As a result, it has become apparent that the overall energy efficiency including process heat recovery turns contrariwise worse by further cancelling even the reduction in the requirements of feedstock and fuel natural gas. The turning point is found to be at a value of the relation (R) to be around 2.25.
- When the relation (R) is made close to 2.0, the primary steam reforming can be effected substantially only by the heat-exchange type reformer. However, a start-up heater is necessary to start-up the heat-exchange type reformer so that further plant investment is required together with the cost-up of the oxygen related apparatus needed in excess. Accordingly, the above-described conditions of the relation (R) = to be close to 2.0 are not economical from the viewpoints of energy efficiency and investment cost.
- In accordance with the cost of natural gas and in consideration of the economical efficiency taking into account primarily apparatus of large equipment costs, including the combustion type steam reforming furnace, air separator and large rotary machines, it has been found that the relation (R) among the mol percentages of CO2, CO and H2 in the synthesis gas should be selected and designed in the range of 2.2 - 2.5.
- As has been described above, according to the present invention, the energy efficiency of a whole process for the production of methanol including the production of synthesis gas is improved in comparison with the conventional processes and the construction cost of the process plant is also reduced.
Claims (4)
- A process for producing methanol which comprises subjecting a feedstock gas comprising hydrocarbons having atomic ratios H/C of hydrogen (H) to carbon (C) of 3 - 4 or a feedstock gas formed by treating hydrocarbons having atomic ratios H/C of 2 - 3 in a prereformer to primary reforming under the conditions of a pressure of 15 - 40 Kg/cm2-G, a catalyst outlet temperature of 750 - 850°C and a molar ratio S/C of steam (S) to carbon (c) in the feedstock gas of 2.5 - 4.0 and then to secondary reforming using oxygen having a purity of 95% or more under the conditions of a pressure of 15 - 40 Kg/cm2-G and a catalyst outlet temperature of 950 - 1,000°C to obtain a synthesis gas in which the relation (R) among the mol percentages of hydrogen, carbon monoxide and carbon dioxide is 2.2 - 2.5 as calculated according to the following equation
- The process according to Claim 1 wherein said combustion gas is obtained by burning a synthesis gas which has been dissolved in methanol discharged from the methanol synthesis and is evolved by reducing the pressure of the methanol to atmospheric pressure, in addition to the part of the feedstock gas and the synthesis purge gas.
- The process according to Claim 1, wherein an effluent gas comprising methanol and unreacted synthesis gas, the heat content of which was recovered by generating steam and which was discharged from the methanol synthesis, is heat-exchanged with the synthesis gas to be introduced into the methanol synthesis to heat said synthesis gas.
- The process according to Claim 1, wherein the synthesis gas discharged from said secondary reformer and heat-exchanged in said heat-exchange type steam reformer is cooled by exchanging heat with water for generating steam used for the heat recovery in the methanol synthesis.
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NL8103397A (en) * | 1981-07-17 | 1983-02-16 | Shell Int Research | METHOD FOR PREPARING ORGANIC COMPOUNDS. |
GB8520567D0 (en) * | 1985-08-16 | 1985-09-25 | British Petroleum Co Plc | Production of synthesis gas |
JP2984720B2 (en) * | 1991-06-10 | 1999-11-29 | 千代田化工建設株式会社 | Methanol synthesis process and plant |
JPH07126201A (en) * | 1993-10-27 | 1995-05-16 | Mitsubishi Gas Chem Co Inc | Methanol production process |
JP2000500428A (en) * | 1995-11-23 | 2000-01-18 | メサノール カサーレ ソシエテ アノニーム | Co-production of ammonia and methanol |
JPH10259148A (en) * | 1997-03-19 | 1998-09-29 | Mitsubishi Heavy Ind Ltd | Production of methanol from synthesis gas |
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- 1998-11-24 JP JP33294198A patent/JP4033988B2/en not_active Expired - Fee Related
- 1998-11-26 WO PCT/JP1998/005317 patent/WO1999028281A1/en active IP Right Grant
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- 1998-11-26 US US09/341,693 patent/US6100303A/en not_active Expired - Lifetime
- 1998-11-26 DE DE69836091T patent/DE69836091T2/en not_active Expired - Lifetime
- 1998-11-26 EP EP98955934A patent/EP1016643B1/en not_active Expired - Lifetime
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US10874983B2 (en) | 2015-12-18 | 2020-12-29 | L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Process and apparatus for the recovery of methanol |
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EP1016643A1 (en) | 2000-07-05 |
JPH11263740A (en) | 1999-09-28 |
JP4033988B2 (en) | 2008-01-16 |
DE69836091T2 (en) | 2007-05-03 |
DE69836091D1 (en) | 2006-11-16 |
EP1016643A4 (en) | 2004-03-31 |
US6100303A (en) | 2000-08-08 |
WO1999028281A1 (en) | 1999-06-10 |
DK1016643T3 (en) | 2007-02-05 |
BR9806130A (en) | 1999-10-26 |
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